High-stability, high-efficiency, and low-cost solar photoelectrochemical (PEC) water splitting has great potential for hydrogen-energy applications. Here, we report on gold/titanium dioxide (Au/TiO2) nanofiber structures grown directly on a conductive indium tin oxide substrate, and used as photoelectrodes in PEC cells for hydrogen generation. The titanium dioxide nanofibers (TiO2 NFs) are synthesized using electrospinning, and are surface-modified by the deposition of gold nanoparticles (Au NPs) using a simple photoreduction method. The structure and morphology of the materials were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The surface plasmon resonance (SPR) of the Au NPs was investigated by ultraviolet-visible (UV-Vis) diffuse reflectance spectroscopy. The PEC properties of the as-prepared photoelectrodes were measured. The obtained photoconversion efficiency of 0.52% under simulated-sunlight illumination by a 150 W xenon lamp of the Au/TiO2 NFs structure with 15 min UV irradiation for Au NP deposition was the highest value from comparable structures. Working photoelectrode stability was tested, and the mechanism of the enhanced PEC performance is discussed.